2-aminothiophene radical substituted by an electron withdrawing group

ABSTRACT

Disazothiphene dyes of the formula   &lt;IMAGE&gt;   where X is an electron withdrawing group, Z is an electron withdrawing group, D is the radical of a diazo component and K is the radical of a coupling component, are highly suitable for dyeing synthetic fibers, in particular polyesters.

SUMMARY OF THE INVENTION

The present invention relates to disazothiophene dyes of the formula I ##STR2## where X is fluorine, chlorine, bromine, hydroxyl, mercapto, C₁ -C₄ -alkoxy which may be substituted by phenyl, C₅ -C₇ -cycloalkoxy, sustituted or unsubstituted phenoxy, C₁ -C₄ -alkylthio which may be substituted by phenyl, C₅ -C₇ -cycloalkylthio, substituted or unsubstituted phenylthio, or SO₂ --E, where E is unsubstituted or phenyl-substituted C₁ -C₈ -alkyl, C₃ -C₄ -alkenyl, C₅ -C₇ -cycloalkyl, substituted or unsubstituted phenyl, chlorine, hydroxyl or C₁ -C₄ -alkoxy which may be substituted by phenyl, or is substituted or unsubstituted phenoxy, amino, C₁ -C₄ -monoalkylamino or -dialkylamino or substituted or unsubstituted phenylamino,

Z is cyano, nitro, C₁ -C₈ -alkanoyl, substituted or unsubstituted benzoyl, C₁ -C₄ -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, carboxyl, or C₁ -C₈ -alkoxycarbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, or is substituted or unsubstituted phenoxycarbonyl, carbamoyl, C₁ -C₈ -monoalkylcarbamoyl or -dialkylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl, piperazinocarbonyl or (N-C₁ -C₄ -alkyl)piperazinocarbonyl,

D is the radical of a diazo component and

K is the radical of a coupling component.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

All the alkyl groups in the formulae of the disazothiophene dyes according to the invention may be straight-chain or branched.

Where substituted phenyl appears in the formulae of the disazothiophene dyes according to the invention, possible substituents are C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen.

Examples of radicals X, in addition to those already mentioned, are OCH₃, OC₂ H₅, OC₃ H₇, OC₄ H₉, OCH₂ C₆ H₅, OC₆ H₁₁, OC₆ H₅, OC₆ H₄ CH₃, OC₆ H₄ Cl, SCH₃, SC₂ H₅, SC₃ H₇, SC₄ H₉, SCH₂ C₆ H₅, SC₂ H₄ OH, SCH₂ CO₂ CH₃, SCH₂ CO₂ C₂ C₂ H₅, SC₆ H₁₁, SC₆ H₅ and SC₆ H₄ CH₃.

Examples of radicals E are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, C₆ H₁₁, C₈ H₁₇, C₆ H₅ --CH₂, C₆ H₅ --CH₂ --CH₂, C₆ H₅, Cl--C₆ H₄, C₄ H₉ --C₆ H₄, Cl, OH, CH₃ O, C₂ H₅ O, C₃ H₇ O, C₄ H₉ O, C₆ H₅ --CH₂ O, C₆ H₅ --CH₂ --CH₂ O, C₆ H₅ O, ClC₆ H₄ O, CH₃ C₆ H₄ O, NH₂, NHCH₃, N(CH₃)₂, NHC₂ H₅, N(C₂ H₅)₂, NHC₄ H₉, N(C₄ H₉)₂, NHC₆ H₅, NHC₆ H₄ --CH₃, NHC₆ H₄ Cl and NCH₃ C₆ H₄.

Examples of radicals Z, in addition to those already mentioned, are CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR3## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, ##STR4## COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂ and ##STR5##

The radicals D of the diazo components are preferably derived from the aniline series or from heterocyclic components for example from the thiophene, thiazole, isothiazole, thiadiazole, benzothiazole or benzisothiazole series.

These diazo components DNH₂ conform to the formula ##STR6## where T¹ and T² are each hydrogen, chlorine, bromine, cyano, CF₃, nitro, C₁ -C₄ -alkyl, C₁ -C₄ - alkoxy, phenoxy, phenyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, benzylsulfonyl, carboxyl, carbamoyl, C₁ -C₄ -monoalkylcarbamoyl or-dialkylcarbamoyl, which may be substituted by hydroxyl, or is sulfamoyl or C₁ -C₄ -monoalkylsulfamoyl or -dialkylsulfamoyl which may be substituted by hydroxyl,

T³ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl or cyano,

T⁴ is hydrogen, C₁ -C₄ -alkyl, substituted or unsubstituted phenyl, thienyl, furyl, halogen, C₁ -C₄ -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, C₁ -C₄ -alkoxy, phenoxy, substituted or unsubstituted C₁ -C₄ -alkylthio or phenylthio,

T⁵ is substituted or unsubstituted C₁ -C₄ -alkyl, or substituted or unsubstituted phenyl,

Y is hydrogen, C.sub. -C₄ -alkyl, substituted or unsubstituted phenyl, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkanoyl, benzoyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylsulfonyl or phenylsulfonyl and

W is cyano, nitro, C₁ -C₄ -alkoxycarbonyl, phenoxycarbonyl, chlorine or bromine and Z has the above mentioned meaning.

Examples of T¹ and T², in addition to those already mentioned, are methyl, ethyl, methoxy, ethoxy, methylcarbonyl, ethoxycarbonyl, ethylsulfonyl, phenylsulfonyl, dimethylcarbamoyl, 2-hydroxyethylcarbamoyl and 2-hydroxypropylsulfamoyl.

Examples of T³, in addition to those already mentioned, are methyl, ethyl, propyl and butyl.

Where T⁴ is substituted C₁ -C₄ -alkylthio, suitable substituents are hydroxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylcarbonyl, cyano or nitro. T⁴ is for example methyl, ethyl, 4-chlorophenyl, thien-2-yl, fur-2-yl, chlorine, bromine, methylsulfonyl, ethylsulfonyl, methoxy, ethoxy, methylthio, ethylthio or 2-hydroxyethylthio.

All the radicals mentioned for T⁵ can be substituted for example by chlorine, bromine, hydroxyl or C₁ -C₄ -alkoxy. C₁ -C₄ -Alkyl can additionally be substituted by phenyl. T⁵ is for example methyl, ethyl, isopropyl, benzyl, 2-phenylethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-chlorophenyl or 2-hydroxyphenyl.

Examples of Y, in addition to those already mentioned, are HCO, CH₃ CO, C₂ H₅ CO, C₆ H₅ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₅, C₆ H₄ CH₃, C₆ H₄ Cl and C₆ H₄ OCH₃.

Examples of W, in addition to those already mentioned, are methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and phenoxycarbonyl.

The radicals K of the coupling components are preferably derived from the aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, preference being given to those which are derived from the pyrazole, pyridine, thiophene, thiazole or pyridone series and in particular from the aniline series.

The coupling components HK conform in particular to the formula ##STR7## R¹ is hydrogen or C₁ -C₄ -alkyl which may be substituted by phenyl, or is substituted or unsubstituted phenyl,

R² is hydrogen or R³,

R³ is substituted or unsubstituted C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl or substituted or unsubstituted phenyl,

R⁴ and R⁵ are each independently of the other hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, substituted or unsubstituted C₁ -C₄ -alkoxycarbonylamino, substituted or unsubstituted benzoylamino or substituted or unsubstituted C₁ -C₆ -alkanoylamino,

R⁶ is cyano, carbamoyl, C₁ -C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl, nitro or C₁ -C₈ -alkoxycarbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, and

R⁷ is halogen, substituted or unsubstituted phenyl or C₁ -C₁₀ -alkyl or-alkoxy, which may be substituted by phenyl and/or whose alkyl chains may each be interrupted by one or more oxygen atoms, or is phenoxy, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -monoalkylamino or -dialkylamino, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₅ -alkanoylamino, C₁ -C₄ -alkoxycarbonylmethyl or cyanomethyl.

Examples of R¹, in addition to those already mentioned, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- or p-tolyl and o-, m- or p-chlorophenyl.

Where R³ is substituted C₁ -C₆ -alkyl, suitable substituents are chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₄ alkoxy-C₁ -C₈ -alkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl.

Specific examples of R³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl, 2-benzoylethyl, cyclopentyl, cyclohexyl, phenyl and 4-methoxyphenyl.

Where R⁴ and R⁵ are each substituted C₁ -C₄ -alkoxycarbonylamino, benzoylamino or C₁ -C₆ -alkanoylamino, possible substituents are in each chlorine, bromine, cyano, methoxy, ethoxy or phenoxy. R⁴ and R⁵ are each for example methyl, ethyl, methoxy, ethoxy, chlorine, bromine, methyl sulfonylamino, dimethylaminosulfonylamino, methoxycarbonylamino, acetylamino or chloroacetylamino.

Examples of R⁶, in addition to those already mentioned, are carbamoyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i- or sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- or i-propoxyethoxycarbonyl, n-, i-or sec-butoxyethoxycarbonyl.

Examples of R⁷ are chlorine, bromine, 4-chlorophenyl, methyl, ethyl, benzyl, phenylethyl, methoxy, ethoxy, 2-methoxyethoxy, 2-butoxyethoxy, benzyloxy, methoxycarbonyl, methylamino, ethylamino, dimethylamino, methylethylamino, methylthio, acetylamino, propionylamino and methoxycarbonylmethyl.

The compounds of the formula I can be prepared in a conventional manner.

For example, disazothiophene dyes of the formula I are obtained by coupling a diazotized amine of the formula II

    D--NH.sub.2                                                (II)

where D has the abovementioned meanings, onto an aminothiophene of the formula III ##STR8## where X and Z each have the abovementioned meanings, and again diazotizing the resulting dye of the formula IV ##STR9## where D, X and Z each have the abovementioned meanings, and coupling onto a coupling component of the formula V

    H--K                                                       (V)

where K has the abovementioned meanings.

The aminothiophenes of the formula III are known from earlier applications DE-A-3,507,421 and DE-A-3,535,134 or can be prepared according to the methods described therein or in conventional manner.

Furthermore, further dyes according to the invention can be prepared by replacing the halogen in dyes of the forumula IV ##STR10## where D, Z and K each have the abovementioned meanings and Hal is halogen, by appropriate radicals Y, for example phenylthio or phenylsulfonyl.

Further details of the preparation of the disazothiophene dyes according to the invention can be found in the Examples.

Dyed up, the novel disazothiophene dyes of the formula I have hues ranging from red to greenish blue. The are suitable for dyeing synthetic fibers, for example polyesters, nylons, cellulose esters or blend fabrics composed of polyesters and cellulose fibers. The dyeings obtained generally have good to very good fastness properties, in particular on polyesters.

Given a suitable constitution, the dyes are also dischargeable under alkaline and/or reducing conditions in a conventional manner.

Particular importance attaches to disazothiophene dyes of the formula I where

X is chlorine, bromine, hydroxyl, mercapto or C₁ -C₄ -alkoxy which may be substituted by phenyl, or is C₅ -C₇ -cycloalkoxy, substituted or unsubstituted phenoxy or C₁ -C₄ -alkylthio which may be substituted by phenyl, or is C₅ -C₇ -cycloalkylthio, substituted or unsubstituted phenylthio or SO₂ --E, where E is methyl, ethyl or phenyl,

Z is cyano or C₁ -C₈ -alkoxycarbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, is the

D radical of a diazo component of the benzene, thiophene or isothiazole series and

K is the radical of a coupling component of the aniline or pyridine series.

Industrially particularly useful compounds of the formula I where

X is chlorine, ethoxy, phenylsulfonyl or phenylmercapto,

Z is cyano,

D is the radical of a diazo component of the benzene series and

K is the radical of a coupling component of the aniline series.

The Examples which follow will illustrate the invention in more detail. The parts and percentages are by weight, unless otherwise stated.

EXAMPLE 1

9.3 parts of aniline were suspended in 50 parts of water, 70 parts by volume of 5 N hydrochloric acid in 100 parts of ice, and the suspension was cooled down to 0° C. a solution of 7.6 parts of NaNO₂ in 33 parts of water were added dropwise. After about 1 hour at 0°-5° C. and after the excess nitrite had been decomposed with sulfamic acid, the diazonium salt solution was gradually added to a suspension of 16.6 parts of 2-amino-4-chloro-3-cyanothiophene in 500 parts by volume of methanol and 500 parts of ice. After about 5 hours at 0°-5° C. the precipitated dye of the formula ##STR11## was filtered off with suction, washed with water until neutral and dried at 50° C. under reduced pressure. 20 parts of dye were obtained.

3.9 parts of this dye were dissolved in 34 parts by volume of 85% strength phosphoric acid and 34 parts by volume of glacial acetic acid. The solution was cooled down to 0° C. 4.95 parts of 40% strength nitrosylsulfuric acid were added. After 1 hour stirring at 0° C. the diazonium salt solution was slowly added dropwise to a solution of 3.2 parts of N-butyl-(N-2-cyanoethyl)aniline in 60 parts by volume of methanol together with about 100 parts of ice and 0.2 part of sulfamic acid. After 2 hours the precipitated dye of the formula ##STR12## was filtered off with suction, washed until neutral and dried. The dye obtained in an amount of 6.2 parts, dyes polyester fabrics in fast navy shades.

EXAMPLE 2

13 parts of 4-chloroaniline were dissolved in 80 parts of water and 30 parts by volume of concentrated hydrochloric acid. 100 parts of ice were added, and the solution was cooled down to 0° C. 7.6 parts of NaNO₂, dissolved in 33 parts of water, were added dropwise. The mixture was stirred at 0°-5° C. for 3 hours. The excess nitrite was then destroyed with sulfamic acid. The diazonium solution was gradually added to a suspension of 16.6 parts of 2-amino-4-chloro-3-cyanothiophene in 500 parts by volume of methanol and 500 parts of ice. After about 6 hours at 0°-5° C. the precipitated dye of the formula ##STR13## was filtered off with suction, washed until neutral and dried (23.2parts).

4.45 parts of this dye were dissolved in 34 parts by volume of 85% strength phosphoric acid and 34 parts by volume of glacial acetic acid. The solution was cooled down to 0° C. 4.95 parts of 40% strength nitrosylsulfuric acid were added. After stirring at 0° C. for an hour the diazonium salt solution was slowly added dropwise to a solution of 2.8 parts of (N-2-cyanoethyl)-N-ethylaniline in 60 parts by volume of methanol together with about 100 parts of ice and 0.2 part of sulfamic acid. After about 3 hours the precipitated dye of the formula ##STR14## was filtered off with suction, washed until neutral and dried. The dye, obtained in an amount of 4.9 parts, dyes polyester fabrics in fast blue shades.

Table 1 below gives further dyes according to the invention which are obtained similarly to the above Examples. The dyes of Table 1 and also those of Tables 2 and 3 below each conform to the formula ##STR15##

                                      TABLE 1                                      __________________________________________________________________________     Ex-                                          Hue on                            ample                                                                              D              X Z    K                  PES                               __________________________________________________________________________                        Cl                                                                               CN                                                                                   ##STR16##         navy                              4                                                                                   ##STR17##     Cl                                                                               CN                                                                                   ##STR18##         navy                              5                                                                                   ##STR19##     Cl                                                                               CN                                                                                   ##STR20##         navy                              6                                                                                   ##STR21##     Cl                                                                               CN                                                                                   ##STR22##         navy                              7                                                                                   ##STR23##     Cl                                                                               CN                                                                                   ##STR24##         blue                              8                                                                                   ##STR25##     Cl                                                                               CN                                                                                   ##STR26##         navy                              9                                                                                   ##STR27##     Cl                                                                               CN                                                                                   ##STR28##         blue                              10                                                                                  ##STR29##     Cl                                                                               CN                                                                                   ##STR30##         blue                              11                                                                                  ##STR31##     Cl                                                                               CN                                                                                   ##STR32##         navy                              12                                                                                  ##STR33##     Cl                                                                               CN                                                                                   ##STR34##         navy                              13                                                                                  ##STR35##     Cl                                                                               CN                                                                                   ##STR36##         navy                              14                                                                                  ##STR37##     Cl                                                                               CN                                                                                   ##STR38##         navy                              15                                                                                  ##STR39##     Cl                                                                               CN                                                                                   ##STR40##         blue                              16                                                                                  ##STR41##     Cl                                                                               CN                                                                                   ##STR42##         blue                              17                                                                                  ##STR43##     Cl                                                                               CN                                                                                   ##STR44##         blue                              18                                                                                  ##STR45##     Cl                                                                               CN                                                                                   ##STR46##         blue                              19                                                                                  ##STR47##     Cl                                                                               CN                                                                                   ##STR48##         blue                              20                                                                                  ##STR49##     Cl                                                                               CN                                                                                   ##STR50##         greenish blue                     21                                                                                  ##STR51##     Cl                                                                               CN                                                                                   ##STR52##         blue                              22                                                                                  ##STR53##     Cl                                                                               CN                                                                                   ##STR54##         blue                              23                                                                                  ##STR55##     Cl                                                                               CN                                                                                   ##STR56##         blue                              24                                                                                  ##STR57##     Cl                                                                               CN                                                                                   ##STR58##         blue                              25                                                                                  ##STR59##     Cl                                                                               CN                                                                                   ##STR60##         blue                              26                                                                                  ##STR61##     Cl                                                                               CN                                                                                   ##STR62##         navy                              27                                                                                  ##STR63##     Cl                                                                               CN                                                                                   ##STR64##         blue                              28                                                                                  ##STR65##     Cl                                                                               CN                                                                                   ##STR66##         navy                              29                                                                                  ##STR67##     Cl                                                                               CN                                                                                   ##STR68##         blue                              30                                                                                  ##STR69##     Cl                                                                               CN                                                                                   ##STR70##         blue                              31                                                                                  ##STR71##     Cl                                                                               CN                                                                                   ##STR72##         blue                              32                                                                                  ##STR73##     Cl                                                                               CN                                                                                   ##STR74##         blue                              33                                                                                  ##STR75##     Cl                                                                               CN                                                                                   ##STR76##         blue                              34                                                                                  ##STR77##     Cl                                                                               CN                                                                                   ##STR78##         bluish green                      35                                                                                  ##STR79##     Cl                                                                               CN                                                                                   ##STR80##         green                             36                                                                                  ##STR81##     Cl                                                                               CN                                                                                   ##STR82##         bluish green                      37                                                                                  ##STR83##     Cl                                                                               CN                                                                                   ##STR84##         blue                              38                                                                                  ##STR85##     Cl                                                                               CN                                                                                   ##STR86##         blue                              39                                                                                  ##STR87##     Cl                                                                               CN                                                                                   ##STR88##         blue                              40                                                                                  ##STR89##     Cl                                                                               CN                                                                                   ##STR90##         blue                              41                                                                                  ##STR91##     Cl                                                                               CN                                                                                   ##STR92##         blue                              42                                                                                  ##STR93##     Cl                                                                               CN                                                                                   ##STR94##         blue                              43                                                                                  ##STR95##     Cl                                                                               CN                                                                                   ##STR96##         blue                              44                                                                                  ##STR97##     Cl                                                                               CN                                                                                   ##STR98##         blue                              45                                                                                  ##STR99##     Cl                                                                               CN                                                                                   ##STR100##        bluish green                      46                                                                                  ##STR101##    Cl                                                                               CN                                                                                   ##STR102##        blue                              47                                                                                  ##STR103##    Cl                                                                               CN                                                                                   ##STR104##        green                             48                                                                                  ##STR105##    Cl                                                                               CN                                                                                   ##STR106##        green                             49                                                                                  ##STR107##    Cl                                                                               CN                                                                                   ##STR108##        green                             50                                                                                  ##STR109##    Cl                                                                               CN                                                                                   ##STR110##        bluish green                      51                                                                                  ##STR111##    Cl                                                                               CN                                                                                   ##STR112##        green                             52                                                                                  ##STR113##    Br                                                                               CN                                                                                   ##STR114##        blue                              53                                                                                  ##STR115##    Cl                                                                               CN                                                                                   ##STR116##        red                               54                                                                                  ##STR117##    Cl                                                                               CN                                                                                   ##STR118##        green                             55                                                                                  ##STR119##    Cl                                                                               CN                                                                                   ##STR120##        bluish green                      56                                                                                  ##STR121##    Cl                                                                               CN                                                                                   ##STR122##        green                             57                                                                                  ##STR123##    Cl                                                                               CN                                                                                   ##STR124##        green                             58                                                                                  ##STR125##    Cl                                                                               CN                                                                                   ##STR126##        green                             59                                                                                  ##STR127##    Cl                                                                               CN                                                                                   ##STR128##        reddish blue                      60                                                                                  ##STR129##    Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                             ##STR130##        navy                              61                                                                                  ##STR131##    Cl                                                                               CO.sub.2 C.sub.4 H.sub.9                                                             ##STR132##        navy                              62                                                                                  ##STR133##    Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                             ##STR134##        blue                              63                                                                                  ##STR135##    Cl                                                                               CO.sub.2 CH.sub.3                                                                    ##STR136##        navy                              64                                                                                  ##STR137##    Cl                                                                               CN                                                                                   ##STR138##        blue                              65                                                                                  ##STR139##    Cl                                                                               CN                                                                                   ##STR140##        blue                              66                                                                                  ##STR141##    Cl                                                                               CN                                                                                   ##STR142##        blue                              __________________________________________________________________________

EXAMPLE 67

7.05 parts of 4-nitroaniline were suspended in 50 parts by volume of 3:1 glacial acetic acid/propionic acid. At 15°-20° C., 60 parts by volume of concentrated sulfuric acid were added, and the mixture was cooled down to 0° C. 16.5 parts of 40% strength nitrosylsulfuric acid were then slowly added dropwise, and the solution was stirred at 0°-5° C. for 4 hours.

To this diazonium salt solution were added dropwise at about 10° C. 9.8 parts of 2-amino-3-cyano-4-ethoxythiophene, suspended in 150 parts by volume of glacial acetic acid. 1 part of sulfamic acid was then added, and the reaction solution was diluted with ice-water to 2000 parts by volume. At 0°-5° the solution was then brought to pH 3.5 with about 38 parts of sodium hydroxide in 100 parts of water. After 4 hours the precipitated dye of the formula ##STR143## was filtered off with suction, washed and dried (14.9 parts).

4.75 parts of this dye were dissolved in 34 parts by volume of 85% strength phosphoric acid and 34 parts by volume of glacial acetic acid. The solution was cooled down to 0° C. 4.95 parts of 40% strength nitrosylsulfuric acid were gradually added. After 1 hour stirring at 0° C. this diazonium salt solution was slowly added dropwise to a solution of 3.2 parts of N-butyl-(N-2-cyanoethyl)aniline in 60 parts by volume of methanol together with about 100 parts of ice and 0.2 part of sulfamic acid. The precipitated dye of the formula ##STR144## was filtered off with suction, washed and dried. The dye, obtained in a yield of 6.1 parts, dyes polyester fabrics in fast bluish green shades.

Table 2 below gives further dyes according to the invention which are obtained similarly to the above Example.

                                      TABLE 2                                      __________________________________________________________________________     Ex-                                       Hue on                               ample                                                                              D           X     Z  K                PES                                  __________________________________________________________________________     68                                                                                  ##STR145## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR146##      navy                                 69                                                                                  ##STR147## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR148##      navy                                 70                                                                                  ##STR149## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR150##      blue                                 71                                                                                  ##STR151## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR152##      navy                                 72                                                                                  ##STR153## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR154##      navy                                 73                                                                                  ##STR155## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR156##      blue                                 74                                                                                  ##STR157## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR158##      blue                                 75                                                                                  ##STR159## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR160##      blue                                 76                                                                                  ##STR161## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR162##      blue                                 77                                                                                  ##STR163## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR164##      blue                                 78                                                                                  ##STR165## OC.sub.2 H.sub.5                                                                     CN                                                                                 ##STR166##      green                                79                                                                                  ##STR167## C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR168##      blue                                 80                                                                                  ##STR169## C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR170##      blue                                 81                                                                                  ##STR171## C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR172##      blue                                 82                                                                                  ##STR173## C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR174##      blue                                 __________________________________________________________________________

EXAMPLE 83

0.62 parts of sodium phenylsulfinate was added to 1.2 parts of the disazo dyes described in Example 1, in 25 parts by volume of N,N-dimethylformamide. After stirring at 25° C. for 12 hours the reaction mixture was discharged onto 300 parts of water, and the dye of the formula ##STR175## was salted out with NaCl, filtered off with suction, washed and dried. The dye, obtained in a yield of 1.4 parts, dyes polyester fibers in fast blue shades.

EXAMPLE 84

0.41 part of thiophenol and 0.7 part by volume of 30% strength methanolic sodium methylate solution were added to 1.2 parts of the disazo dye described in Example 1, in 25 parts by volume of N,N-dimethylformamide. After stirring at 25° C. for 24 hours the reaction mixture was discharged onto 300 parts of water. The dye of the formula ##STR176## was salted out with NaCl, filtered off with suction, washed and dried. The dye, obtained in a yield of 1.3 parts, dyes polyester fibers in fast blue shades.

Table 3 below gives further dyes according to the invention which are obtained similarly to the above Examples.

                                      TABLE 3                                      __________________________________________________________________________     Ex-                                      Hue on                                ample                                                                              D          X     Z  K                PES                                   __________________________________________________________________________     85                                                                                  ##STR177##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR178##      blue                                  86                                                                                  ##STR179##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR180##      blue                                  87                                                                                  ##STR181##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR182##      blue                                  88                                                                                  ##STR183##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR184##      blue                                  89                                                                                  ##STR185##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR186##      blue                                  90                                                                                  ##STR187##                                                                               C.sub.6 H.sub.5SO.sub.2                                                              CN                                                                                 ##STR188##      blue                                  91                                                                                  ##STR189##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR190##      blue                                  92                                                                                  ##STR191##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR192##      blue                                  93                                                                                  ##STR193##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR194##      blue                                  94                                                                                  ##STR195##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR196##      blue                                  95                                                                                  ##STR197##                                                                               CH.sub.3 S                                                                           CN                                                                                 ##STR198##      blue                                  96                                                                                  ##STR199##                                                                               C.sub.2 H.sub.5 S                                                                    CN                                                                                 ##STR200##      blue                                  97                                                                                  ##STR201##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR202##      blue                                  98                                                                                  ##STR203##                                                                               C.sub.6 H.sub.5 O                                                                    CN                                                                                 ##STR204##      blue                                  99                                                                                  ##STR205##                                                                               C.sub.6 H.sub.5 S                                                                    CN                                                                                 ##STR206##      blue                                  __________________________________________________________________________ 

We claim:
 1. A disazothiophene dye of the formula ##STR207## wherein: X which is an electron withdrawing group is fluorine, chlorine, bromine, hydroxyl, mercapto, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy substituted by phenyl, C₅ -C₇ -cycloalkoxy, phenoxy, phenoxy substituted by methyl or chlorine, C₁ -C₄ -alkylthio, C₁ -C₄ -alkythio substituted by phenyl, C₅ -C₇ -cyloalkylthio, phenylthio, phenylthio substituted by methyl, or SO₂ --E, where E is C₁ -C₄ -alkyl, phenylsubstituted C₁ -C₈ -alkyl, C₃ -C₄ -alkenyl, C₅ -C₇ -cycloalkyl, phenyl, phenyl substituted by chlorine or butyl, chlorine, hydroxyl, C₁ -C₄ -alkoxy, or C₁ -C₄ -alkoxy substituted by phenyl, or E is phenoxy, phenoxy substituted by chlorine or methyl, amino, C₁ -C₄ -monoalkylamino or C₁ -C₄ -dialkylamino or phenylamino, phenylamino substituted by chlorine or methyl,Z is cyano, nitro, C₁ -C₈ -alkanoyl, benzoyl, benzoyl substituted by one or two methyl, one or two chlorine, or methoxy, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, phenylsulfonyl substituted by chlorine or methyl, carboxyl, C₁ -C₈ -alkoxycarbonyl, or C₁ -C₈ -alkoxycarbonyl whose alkyl chain is interrupted by one oxygen atom, or is phenoxycarbonyl, phenoxycarbonyl substituted by methyl, carbamoyl, C₁ -C₈ -monoalkylcarbamoyl or C₁ -C₈ -dialkylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl, piperazinocarbonyl or (N-C₁ -C₄ -alkyl)piperazinocarbonyl, D is the radical of a diazo component, and K is the radical of a coupling component.
 2. The disazothiophene of claim 1, where D is derived from a diazo component of the formula ##STR208## where T¹ and T² are each independently hydrogen, chlorine, bromine, cyano, CF₃, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, phenyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, carboxyl, carbamoyl, C₁ -C₄ -monoalkylcarbamoyl, C₁ -C₄ -dialkylcarbamoyl, C₁ -C₄ -monoalkylcarbamoyl substituted by hydroxyl, or C₁ -C₄ -dialkylcarbamoyl substituted by hydroxyl, or T¹ and T² are each independently sulfamoyl, C₁ -C₄ -monoalkylsulfamoyl, C₁ -C₄ -dialkylsulfamoyl, C₁ -C₄ -monoalkylsulfamoyl substituted by hydroxyl, or C₁ -C₄ -dialkylsulfamoyl substituted by hydroxyl,T³ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl or cyano, T⁴ is hydrogen, C₁ -C₄ -alkyl, phenyl, phenyl substituted by chlorine, thienyl, furyl, halogen, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₄ -alkylthio C₁ -C₄ -alkylthio substituted by hydroxyl, C₁ -C₄ -alkylcarbonyl, cyano or nitro, or phenylthio, T⁵ is C₁ -C₄ -alkyl, C₁ -C₄ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy or phenyl, phenyl, or phenyl substituted by chlorine, bromine, hydroxyl, or C₁ -C₄ -alkoxy, Y is hydrogen, C₁ -C₄ -alkyl, phenyl, phenyl substituted by methyl, methoxy or chlorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkanoyl, benzoyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylsulfonyl or phenylsulfonyl, and W is cyano, nitro, C₁ -C₄ -alkoxycarbonyl, phenoxycarbonyl, chlorine or bromine.
 3. The disazothiophene dye of claim 1, where K is derived from a coupling component of the formulae ##STR209## wherein: R¹ is hydrogen, C₁ -C₄ -alkyl, or C₁ -C₄ -alkyl substituted by phenyl, phenyl, phenyl substituted by methyl or chlorine,R² is hydrogen or R³, R³ is C₁ -C₆ -alkyl, C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₄ -alkoxy-C₁ -C₈ -alkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl, or R³ is C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl, phenyl, or methoxyphenyl, R⁴ and R⁵ are each independently of the other hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, C₁ -C₄ -alkoxycarbonylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy C₁ -C₄ -alkoxycarbonylamino, benzoylamino, benzoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, or C₁ -C₆ -alkanoylamino, C₁ -C₆ -alkanoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, R⁶ is cyano, carbamoyl, C₁ -C₄ -monoalkylcarbamoyl or C₁ -C₄ -dialkylcarbamoyl, nitro, C₁ -C₈ -alkoxycarbonyl, or C₁ -C₈ -alkoxycarbonyl whose alkyl chain is interrupted by one oxygen atom, and R⁷ is halogen, phenyl, phenyl substituted by chlorine, or C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkyl substituted by phenyl or whose alkyl chains are interrupted by one oxygen atom, or C₁ -C₁₀ -alkoxy substituted by phenyl or whose alkyl chains are interrupted by one oxygen atom, or is phenoxy, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -monoalkylamino or C₁ -C₄ -dialkylamino, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₅ -alkanoylamino, C₁ -C₄ -alkoxycarbonylmethyl or cyanomethyl.
 4. The disazothiophene dye of claim 1, wherein:X which is an electron withdrawing group is chlorine, bromine, hydroxyl, mercapto, C₁ -C₄ -alkoxy, or C₁ -C₄ -alkoxy substituted by phenyl, or is C₅ -C₇ -cycloalkoxy, phenoxy, phenoxy substituted by chlorine or methyl, C₁ -C₄ -alkylthio, or C₁ -C₄ -alkylthio substituted by phenyl, or is C₅ -C₇ -cycloalkylthio, phenylthio, phenylthio substituted by methyl, or SO₂ --E, where E is methyl, ethyl or phenyl, Z is cyano, C₁ -C₈ -alkoxycarbonyl, or C₁ -C₈ alkoxycarbonyl whose alkyl chain is interrupted by one oxygen atom, D is the radical of a diazo component of the benzene, thiophene or isothiazole series, and K is the radical of a coupling component of the aniline or pyridine series.
 5. The disazothiophene dye of claim 1, wherein said substituted phenyl is phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen.
 6. The disazothiophene dye of claim 1, wherein X which is an electron withdrawing group is OCH₃, OC₂ H₅, OCH₃ H₇, OC₄ H₉, OCH₂ C₆ H₅, OC₆ H₁₁, OC₆ H₅, OC₆ H₄ CH₃, OC₆ H₄ Cl, SCH₃, SC₂ H₅, SC₃ H₇, SC₄ H₉, SCH₂ C₆ H₅, SC₂ H₄ OH, SCH₂ CO₂ CH₃, SCH₂ CO₂ C₂ H₅, SC₆ H₁₁, SC₆ H₅ or SC₆ H₄ CH₃.
 7. Th disazothiophene dye of claim 1, wherein E is CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, C₆ H₁₁, C₈ H₁₇, C₆ H₅ --CH_(2--CH) ₂, C₆ H₅, Cl--C₆ H₄, C₄ H₉ --C₆ H₄, Cl, OH, CH₃ O, C₂ H₅ O, C₃ H₇ O, C₄ H₉ O, C₆ H₅ --CH₂ O, C₆ H₅ --CH₂ --CH₂ O, C₆ H₅ O, ClC₆ H₄ O, CH₃ C₆ H₄ O, NH₂, NHCH₃, N(CH₃)₂, NHC₂ H₅, N(C₂ H₅)₂, NHC₄ H₉, N(C₄ H₉)₂, NHC₆ H₅, NHC₆ H₄ --CH₃, NHC₆ H₄ Cl or NCH₃ C₆ H₄.
 8. The disazothiophene dye of claim 1, wherein Z is CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, COCH(C₂ H₅)(C₄ H₉) C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, COOCH₂ CH(C₂ H₅)(C₄ H₉) COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC.sub. 6 H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(CH₃)(C₂ H₅).
 9. The disazothiophene dye of claim 2, wherein T¹ or T² is methyl, ethyl, methoxy, ethoxy, methylcarbony, ethoxycarbonyl, ethylsulfonyl, phenylsulfonyl, dimethylcarbamoyl, 2-hydroxyethylcarbamoyl or 2-hydroxypropylsulfamoyl.
 10. The disazothiophene dye of claim 2, wherein T³ is methyl, ethyl, propyl, or butyl.
 11. The disazothiophene dye of claim 2, wherein T⁴ is C₁ -C₄ -alkylthio substituted by hydroxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylcarbonyl, cyano, nitro, methyl, ethyl, 4-chlorophenyl, thien-2-yl, fur-2-yl, chlorine, bromine, methylsulfonyl, ethylsulfonyl, methoxy, ethoxy, methylthio, ethylthio, or 2-hydroxyethylthio.
 12. The disazothiophene dye of claim 2, wherein T⁵ is C₁ -C₄ -alkyl substituted by chlorine, bromine, hydroxyl, or C₁ -C₄ -alkoxy.
 13. The disazothiophene dye of claim 2, wherein T⁵ is phenyl substituted by chlorine, bromine, hydroxyl, or C₁ -C₄ -alkoxy.
 14. The disazothiophene dye of claim 2, wherein T⁵ is C₁ -C₄ -alkyl substituted by phenyl.
 15. The disazothiophene dye of claim 2, wherein T⁵ is methyl, ethyl, isopropyl, benzyl, 2-phenylethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-chlorophenyl or 2-hydroxyphenyl.
 16. The disazothiophene dye of claim 2, wherein Y is HCO, CH₃ CO, C₆ H₅ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₅, C₆ H₄ CH₃, C₆ H₄ Cl and C₆ H₄ OCH₃.
 17. The disazothiophene dye of claim 2, wherein W is methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl or phenoxycarbonyl.
 18. The disazothiophene dye of claim 3, wherein R¹ is methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- or p-tolyl or o-, m- or p-chlorophenyl.
 19. The disazothiophene dye of claim 3, wherein R³ is C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzyloxy, o-, m - or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₄ -alkoxy-C₁ -C₈ -alkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxycarbonyl phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl.
 20. The disazothiophene dye of claim 3, wherein R³ is methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2methlaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl, 2-benzoylethyl, cyclopentyl, cyclohexyl, phenyl or 4-methoxyphenyl.
 21. The disazothiophene dye of claim 3, wherein R⁴ or R⁵ is C₁ -C₄ -alkoxy-carbonylamino, benzoylamino or C₁ -C₆ -alkanoylamino each substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy.
 22. The disazothiophene dye of claim 3, wherein R⁴ or R⁵ is methyl, ethyl, methoxy, ethoxy, chlorine, bromine, methyl sulfonylamino, dimethylaminosulfonylamino, methoxycarbonylamino, acetylamino or chloroacetylamino.
 23. The disazothiophene dye of claim 3, wherein R⁶ is carbamoyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n-or i-propoxycarbonyl, n-, i- or sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n-or i-propoxyethoxycarbonyl, or n-, i- or sec-butoxyethoxycarbonyl.
 24. The disazothiophene dye of claim 3, wherein R⁷ is chlorine, bromine, 4-chlorophenyl, methyl, ethyl, benzyl, phenylethyl, methoxy, ethoxy, 2-methoxyethoxy, 2-butoxyethoxy, benzyloxy, methoxycarbonyl, methylamino, ethylamino, dimethylamino, methylethylamino, methylthio, acetylamino, propionylamino and methoxycarbonylmethyl. 